EP0296861B1 - Improvements in or relating to laminated metal structures for resisting wear at elevated temperatures - Google Patents

Improvements in or relating to laminated metal structures for resisting wear at elevated temperatures Download PDF

Info

Publication number
EP0296861B1
EP0296861B1 EP88305747A EP88305747A EP0296861B1 EP 0296861 B1 EP0296861 B1 EP 0296861B1 EP 88305747 A EP88305747 A EP 88305747A EP 88305747 A EP88305747 A EP 88305747A EP 0296861 B1 EP0296861 B1 EP 0296861B1
Authority
EP
European Patent Office
Prior art keywords
layer
hard
base metal
buttering
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88305747A
Other languages
German (de)
French (fr)
Other versions
EP0296861A1 (en
Inventor
Javaid Iqbal Qureshi
Michael Earl Anderson
Roland Henry Kaufman
William Lester Spahr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CBS Corp
Original Assignee
Westinghouse Electric Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Westinghouse Electric Corp filed Critical Westinghouse Electric Corp
Publication of EP0296861A1 publication Critical patent/EP0296861A1/en
Application granted granted Critical
Publication of EP0296861B1 publication Critical patent/EP0296861B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/001Interlayers, transition pieces for metallurgical bonding of workpieces
    • B23K35/004Interlayers, transition pieces for metallurgical bonding of workpieces at least one of the workpieces being of a metal of the iron group
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3046Co as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/939Molten or fused coating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49316Impeller making
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49316Impeller making
    • Y10T29/49318Repairing or disassembling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12931Co-, Fe-, or Ni-base components, alternative to each other
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12937Co- or Ni-base component next to Fe-base component

Definitions

  • This invention relates to turbine components having laminated metal structures for resisting wear at elevated temperatures.
  • Turbine components used in electrical power generation generally encounter severe wear due to a variety of mechanisms including: abrasion, erosion, fretting, corrosion, and metal-to-metal friction.
  • abrasion, erosion, fretting, corrosion, and metal-to-metal friction are especially susceptible to this phenomenon.
  • Such parts are typically manufactured from stainless steel, i.e., 12% Cr material. Since this metal is not hard in its tempered condition (15 to 25 Rockwell "C"), protective coatings such as hard facings or claddings are usually employed to prolong the life of these parts in service.
  • STELLITE "6" STELLITE is a Registered Trade Mark, (RTM), which is a is an extremely hard material that has been a standard for hard-surfacing applications. It generally produces a surface which resists metal-to-metal wear, abrasion and impact.
  • RTM Registered Trade Mark
  • STELLITE is often associated with cracking due, in part, to the differences between the coefficient of thermal expansion between the 12% Cr base metal and the welded deposit. Moreover, such cracking can also extend into the base metal, which often has been hardened intensely from the welding temperatures. This can lead to the premature failure of the component and necessitate its repair or replacement.
  • TRIBALOY (RTM) 400 from Cabot Corp. of Kokomo, Ind.
  • TRIBALOY is a cobalt-based alloy and therefore retains its hardness even at elevated temperatures. See T. B. Jefferson, et al., Metals and How to Weld Them , James F. Lincoln Arc Welding Foundation, Cleveland, OH, February, 1983. Deposits of TRIBALOY and the heat affected zone of the underlying 12% Cr stainless steel base metal, unfortunately, have developed cracks and pin holes after welding, and therefore, are not completely satisfactory.
  • Birchfield also discloses the following examples: high-nickel weld metal deposited on a carbon or low-alloy steel substrate, to be welded later to a high-alloy steel base metal; a nickel-chromium-iron alloy deposited on a stainless-clad low-alloy steel before welding to stainless steel.
  • this reference fails to address the problems associated with the thermal shock and base metal cracking of turbine components.
  • this reference requires that the buttering layer be welded to a separate buttering part prior to attachment to a base metal mating part.
  • US-A-4,665,996 discloses a method of reducing friction between a drill string and casing during a rotary drilling operation.
  • the cobalt-molybdenum alloys employed serve both to hard face the drill string and reduce friction during drilling operations.
  • a TRIBALLOY 800 hardfacing layer and a INCONEL 600 buttering layer is welded to a type 304 stainless steel.
  • the present invention resides in a turbine component having a laminated metal structure for resisting wear at elevated temperatures which comprises a base metal comprising stainless steel containing 8 to 16 weight percent chromium, a buttering layer welded to said base metal and containing nickel, a nickel-based alloy or a mixture thereof and welded to said buttering layer a hard-surfacing layer comprising cobalt for protecting said base metal from wear at elevated temperatures, and having a macro-hardness of at least 30 R C , characterized in that said buttering layer includes chromium in an amount of at least 12 weight % and said hard-surfacing layer combining with said buttering layer to form a coating substantially free of welding-induced cracks.
  • the laminated metal structure protects the relatively soft stainless steel base metal, which is often subjected to metal-to-metal friction at temperatures above about 900°F (482°C).
  • the buttering layer interposed between the base metal and hard-surfacing layer, is composed of nickel, nickel-based alloys, or a mixture of the two. These materials are chosen for the buttering layer because nickel and its alloys have coefficients of thermal expansion which lie between that for the stainless steel base layer and that of most hard-surfacing materials commonly used in turbine applications.
  • the hard-surfacing layer preferably comprises cobalt to maintain the high temperature hardness of the laminated metal structure under power-generating service conditions.
  • a laminated metal structure 100 which is designed for resisting wear, especially at elevated temperatures.
  • the structure of Fig. 1 can represent, for example, a section of a turbine component such as a key or liner.
  • the structure 100 comprises a base metal 10 comprising stainless steel. Bonded to the base metal 10, is a buttering layer 20 which consists essentially of nickel, a nickel-based alloy or a mixture thereof. Superposed upon the buttering layer is a hard-surfacing layer 30 of commonly used hard-surfacing material, but which preferably comprises cobalt for improved high temperature hardness.
  • the combination of the buttering layer 20 and the hard-surfacing layer 30 of this invention form a substantially continuous coating for protecting the base metal 10 from wear at elevated temperatures.
  • “coating” refers to any mechanical or metallurgical bonding of metal to the base metal 10, and includes deposits produced by cladding, welding or thermal spraying.
  • the base metal 10 is preferably chromium stainless steel containing about 8 to 16% chromium.
  • this material refers to a group of stainless steels that contain no nickel. This group is frequently called “straight chromes" or martensitic stainless steels.
  • straight chromes or martensitic stainless steels.
  • martensitic nature of the steel will greatly depend on the carbon content, a high carbon content tending to make the steel more martensitic.
  • Such steels are generally assumed to be heat treatable and comprise the stainless steel specification numbers AISI 403, AISI 410, AISI 414, AISI 416, AISI 418 Special, 420, 420Se, 431, AISI 440A, AISI 440B, AISI 440C, and AISI 440Se.
  • the materials of this series because of their alloy balance, are capable of hardening intensely from welding temperatures, even with an air cool, and unless precautions are taken, they (and the weld materials used with them) can crack because of the high hardness developed. Preheating the steels, however, can lower thermal differences, and allowing the steel to cool slowly will reduce the cracking tendencies. It is important to the purposes of this invention that the base metal and welded structure remain as crack-free as possible to avoid failure.
  • the hard-surfacing technique is also useful on mild steel, alloyed steel, high carbon steel, and/or a combination of these.
  • the preferred base metal 10 of this laminated metal structure is stainless steel, and more preferably 12% Cr stainless steel.
  • the buttering layer 20 in a soft material having a thermal expansion coefficient between that of the base metal and that of the hard-surfacing layer.
  • the buttering layer consists essentially of nickel, a nickel-based alloy, or a mixture of these.
  • the buttering layer 20 is bonded, preferably welded, to the base metal 10.
  • the buttering layer 20 also adds to the overall strength of the structure, since the bond between the hard-surfacing layer 30 and the base metal 10 may not be strong enough by itself to keep a multi-layer hard-surfacing deposit from pulling off. See T. B. Jefferson, et al., Metals and How to Weld Them , pp. 297, 298.
  • the buttering layer is selected to be a relatively soft material to withstand the shock of the thermal expansion caused by the heat of the welding procedures.
  • Nickel and its alloys are as the preferred metals for the buttering layer 20 of this invention because the coefficient of thermal expansion of these materials is in-between that of the preferred 12% Cr base metal and the preferred hard-surfacing materials.
  • Nickel and nickel alloys are additionally preferred because of their excellent resistance to corrosion and oxidation even at high temperatures and because they permit an overlay of the preferred hard-surfacing materials without significant cracking.
  • the buttering layer 20 should also contain above about 12% chromium by weight. This prevents the diffusion of chromium from the 12% Cr stainless steel into the weld deposit during welding and preserves the corrosion resistance of the base metal 10.
  • MONEL RTM
  • RTM MONEL
  • K MONEL, H MONEL, S MONEL, R MONEL and N MONEL The most preferred material for the buttering layer 20 is INCONEL (RTM) which is a nickel-chromium alloy.
  • the buttering layer 20 generally has a thickness of about 0.25 mm to 5.0 mm, more preferably about 2 mm. This thickness can be attained by machining the layer after bonding to the base metal.
  • the material selected for the hard-surfacing layer 30 should have a Rockwell hardness reading significantly higher than that for the base metal, preferably in the range of 30-55 HRC.
  • the choice of hard-surfacing materials can be made on the basis of service requirements and the nature of wear and other conditions that are expected.
  • Typical hard-surfacing alloys useful for this invention include chromium carbide, tungsten carbide, high-carbon chromium alloy, austenitic manganese, austenitic stainless steel (chromium-nickel types), high-speed tool steels, air or oil hardening tool steels, medium carbon and alloy steels, cobalt-based hard-surfacing materials and nickel-based hard-surfacing alloys.
  • the hard-surfacing alloys preferably comprise cobalt to impart to the finished turbine component high hardness at elevated temperatures.
  • the most preferred materials are TRIBALOY-400 and STELLITE-6, the former being selected as a preferred material for stationary turbine components and the latter being preferred for moving turbine components. While STELLITE-6 is conventional, TRIBALOY-400 is a relatively new alloy consisting essentially of .02 weight %C; 2.6 weight %Si; 8.5 weight %Cr; 28.5 weight %Mo; 3.0 weight %Ni and Fe; and the balance being Co. These materials have been selected for example only, and those skilled in the art may find various alloy substitutions exhibiting similar properties.
  • the hard-surfacing layer of this invention preferably has a thickness of about 1.27 to 6.35 mm, and more preferably about 4.57 mm.
  • the buttering layer 20 and hard-surfacing layer 30 can be bonded to or disposed on the base metal 10 by any mechanical, metallurgical, or chemical means known to those in the metal-working industry.
  • the buttering layer 20 is weld deposited to the base metal layer and the hard-surfacing layer 30, in turn, is weld deposited to the buttering layer.
  • Typical coating processes that can be employed for this purpose include: Thermal Spraying, Plasma Transferred-Arc, Shielded Metal Arc, MIG, or TIG procedures.
  • the most preferred welding process is TIG (Tungsten-Inert-Gas).
  • INCONEL-82 is welded to the base metal, using the above procedure, to provide a buttering layer thickness of about 2.54 mm.
  • the buttering layer is preferably machined to a thickness of about 2.03 mm.
  • the resultant intermediate composite, which comprises the base metal and buttering layer is then heated to a temperature of about 232°C to 482°C, preferably about 400°C, prior to and during the welding of the hard-surfacing layer 30 onto buttering layer 20.
  • the temperature of the substrate during the welding of the hard-surfacing layer 30 is referred to as the "interpass temperature".
  • Preheating is useful to (1) minimize the possibility of thermal shock damage to the stainless steel as the welding arc is applied; (2) slow the cooling to prevent the formation of excessively large fusion zones; (3) prevent excessive hardness in the weld itself; and (4) equalize the cooling of the weld and the base metal, thereby minimizing the possibility of shrinkage cracks.
  • the laminated metal structure is preferably tempered with a post-weld heat treatment.
  • the temperature selected for the post-weld heat treatment should be high enough to temper martensite formations in this base metal.
  • the preferred heat treatment schedule comprises heating the welded structure for a time that is sufficient to relieve at least the maximum stresses caused by the various bonding steps of the method.
  • a preferred heat treatment range is from 593°C to 627°C.
  • the laminated metal structure 100 resulting from the bonding operation, as described, is generally at a temperature of about 232-482°C.
  • the structure can be permitted to cool in an insulating atmosphere, or maintained at about its interpass temperature prior to insertion into a heat-treating oven.
  • the laminated metal structure 100 is then heated at about 30-40°C per hour, preferably about 38° per hour, until is obtains a uniform temperature of about 593°C to 627°C.
  • the structure 100 is then held at that temperature for about 1 to 3 hours.
  • the structure is held at the optimum temperature for one hour per inch of thickness of the component, with one hour being the minimum holding time for pieces under one inch in thickness.
  • the component is preferably allowed to cool at a rate below about 38°C per hour.
  • this invention provides a turbine component having a laminated metal structure 100 exhibiting fewer imperfections, while at the same time, maintaining resistance to wear from room temperature to elevated temperatures.
  • the preferred combination of INCONEL 82 and TRIBALOY 400 produces a surface having a Rockwell "C" hardness reading of about 40-50.
  • the INCONEL 82 buttering layer possesses a coefficient of thermal expansion intermediate to that of the base metal and the preferred hard-surfacing material, TRIBALOY-400.
  • INCONEL 82 also consists of 18.0 to 22.0 weight % Cr which permits the deposition of this alloy with minimal dilution of the chromium content of the stainless steel base metal.
  • the turbine component having a laminated metal structure of this invention is readily fabricated using existing welding procedures and provides for longer lasting turbine components.
  • This structure is particularly useful in minimizing cracking and the service life of stainless steel keys and liners located on the flow guides of steam turbine systems.
  • These components can be coated with a nickel-containing, buttering layer, of the kind described above, then hard-surfaced. Accordingly, the elevated temperature turbine system, thus protected, can be operated with less downtime due to replacement of these critical parts.
  • this invention provides an improved turbine component having a laminated metal structure and method for resisting wear at elevated temperatures.
  • the turbine component having a laminated metal structure utilizes a novel buttering layer which provides a buffer and limits the thermal shock caused by the welding processes. Accordingly, this invention provides a sounder hard-surfacing weldment and specifically, a more economical TRIBALOY application procedure without a high rejection rate due to cracking of weld deposits.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Arc Welding In General (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Physical Vapour Deposition (AREA)

Description

  • This invention relates to turbine components having laminated metal structures for resisting wear at elevated temperatures.
  • Turbine components used in electrical power generation generally encounter severe wear due to a variety of mechanisms including: abrasion, erosion, fretting, corrosion, and metal-to-metal friction. Especially susceptible to this phenomenon are the keys and liners on the steam flow guides located on the upper and lower casing of a high pressure turbine. Such parts are typically manufactured from stainless steel, i.e., 12% Cr material. Since this metal is not hard in its tempered condition (15 to 25 Rockwell "C"), protective coatings such as hard facings or claddings are usually employed to prolong the life of these parts in service.
  • One such coating employed is STELLITE "6" STELLITE is a Registered Trade Mark, (RTM), which is a is an extremely hard material that has been a standard for hard-surfacing applications. It generally produces a surface which resists metal-to-metal wear, abrasion and impact. However, STELLITE is often associated with cracking due, in part, to the differences between the coefficient of thermal expansion between the 12% Cr base metal and the welded deposit. Moreover, such cracking can also extend into the base metal, which often has been hardened intensely from the welding temperatures. This can lead to the premature failure of the component and necessitate its repair or replacement.
  • Replacement of these worn, fretted, or cracked components can be extremely costly. Downtime alone can amount to $100,000 per day, since the electric utility often must buy electrical power elsewhere to meet consumer demands. In addition to this cost, the expenses associated with hiring a repair crew and purchasing and storing spare parts can be significant.
  • In an effort to reduce downtime and the consequent expense, new alloys are currently being developed to prolong the service life of turbine components. One such alloy is TRIBALOY (RTM) 400 from Cabot Corp. of Kokomo, Ind. TRIBALOY is a cobalt-based alloy and therefore retains its hardness even at elevated temperatures. See T. B. Jefferson, et al., Metals and How to Weld Them, James F. Lincoln Arc Welding Foundation, Cleveland, OH, February, 1983. Deposits of TRIBALOY and the heat affected zone of the underlying 12% Cr stainless steel base metal, unfortunately, have developed cracks and pin holes after welding, and therefore, are not completely satisfactory.
  • For producing metallurgically sound weld deposits. the welding industry has traditionally relied on a "buttering" layer. Buttering has been disclosed in the trade literature as a means for applying a transition alloy to a base metal that will later be welded to a part of a different chemical composition. Birchfield, Part Worn or Undersized Metal Overlays Save the Day, Welding Design and Fabrication, pp. 38-48, February, 1985. The Birchfield article reviews various processes and materials for the selection of metal overlaying. It discloses that buttering provides a metallurgical bridge between different alloys and that a buttering material must be readily weldable to the base metal and compatible with the joint filler metal that will unite the buttering part and mating part. Birchfield, also discloses the following examples: high-nickel weld metal deposited on a carbon or low-alloy steel substrate, to be welded later to a high-alloy steel base metal; a nickel-chromium-iron alloy deposited on a stainless-clad low-alloy steel before welding to stainless steel. Although teaching a use for a buttering layer, this reference fails to address the problems associated with the thermal shock and base metal cracking of turbine components. Moreover, this reference requires that the buttering layer be welded to a separate buttering part prior to attachment to a base metal mating part.
  • US-A-4,665,996 (Foroulis et al) discloses a method of reducing friction between a drill string and casing during a rotary drilling operation. The cobalt-molybdenum alloys employed serve both to hard face the drill string and reduce friction during drilling operations. In one application a TRIBALLOY 800 hardfacing layer and a INCONEL 600 buttering layer is welded to a type 304 stainless steel.
  • Accordingly, there is still a need for a method for hard-surfacing metal surfaces to provide turbine components having an extended useful life. There is also a need for a repair procedure that minimizes latent welding stresses and cracking of stainless steel, on power generation equipment.
  • Accordingly, the present invention resides in a turbine component having a laminated metal structure for resisting wear at elevated temperatures which comprises a base metal comprising stainless steel containing 8 to 16 weight percent chromium, a buttering layer welded to said base metal and containing nickel, a nickel-based alloy or a mixture thereof and welded to said buttering layer a hard-surfacing layer comprising cobalt for protecting said base metal from wear at elevated temperatures, and having a macro-hardness of at least 30 RC, characterized in that said buttering layer includes chromium in an amount of at least 12 weight % and said hard-surfacing layer combining with said buttering layer to form a coating substantially free of welding-induced cracks.
  • The laminated metal structure protects the relatively soft stainless steel base metal, which is often subjected to metal-to-metal friction at temperatures above about 900°F (482°C). The buttering layer, interposed between the base metal and hard-surfacing layer, is composed of nickel, nickel-based alloys, or a mixture of the two. These materials are chosen for the buttering layer because nickel and its alloys have coefficients of thermal expansion which lie between that for the stainless steel base layer and that of most hard-surfacing materials commonly used in turbine applications. The hard-surfacing layer preferably comprises cobalt to maintain the high temperature hardness of the laminated metal structure under power-generating service conditions.
  • In order that the invention can be more clearly understood, convenient embodiments thereof will now be described, by way of example, with reference to the accompanying drawing which is a perspective sectional view of a laminated metal structure.
  • With reference to Fig. 1, there is shown a laminated metal structure 100 which is designed for resisting wear, especially at elevated temperatures. The structure of Fig. 1 can represent, for example, a section of a turbine component such as a key or liner. The structure 100 comprises a base metal 10 comprising stainless steel. Bonded to the base metal 10, is a buttering layer 20 which consists essentially of nickel, a nickel-based alloy or a mixture thereof. Superposed upon the buttering layer is a hard-surfacing layer 30 of commonly used hard-surfacing material, but which preferably comprises cobalt for improved high temperature hardness. The combination of the buttering layer 20 and the hard-surfacing layer 30 of this invention form a substantially continuous coating for protecting the base metal 10 from wear at elevated temperatures. As used herein, "coating" refers to any mechanical or metallurgical bonding of metal to the base metal 10, and includes deposits produced by cladding, welding or thermal spraying.
  • The base metal 10 is preferably chromium stainless steel containing about 8 to 16% chromium. Generally, this material refers to a group of stainless steels that contain no nickel. This group is frequently called "straight chromes" or martensitic stainless steels. However, the martensitic nature of the steel will greatly depend on the carbon content, a high carbon content tending to make the steel more martensitic. Such steels are generally assumed to be heat treatable and comprise the stainless steel specification numbers AISI 403, AISI 410, AISI 414, AISI 416, AISI 418 Special, 420, 420Se, 431, AISI 440A, AISI 440B, AISI 440C, and AISI 440Se. The basic type based in the manufacture of turbine components, i.e. keys and liners, is AISI 410 or AISI 403, each of which has a chromium content of about 12%. The materials of this series, because of their alloy balance, are capable of hardening intensely from welding temperatures, even with an air cool, and unless precautions are taken, they (and the weld materials used with them) can crack because of the high hardness developed. Preheating the steels, however, can lower thermal differences, and allowing the steel to cool slowly will reduce the cracking tendencies. It is important to the purposes of this invention that the base metal and welded structure remain as crack-free as possible to avoid failure.
  • Although a straight 12% Cr material such as AISI 403 or AISI 410 is preferred for use as the base material of this invention, the hard-surfacing technique is also useful on mild steel, alloyed steel, high carbon steel, and/or a combination of these. However, since the turbine power generation environment is corrosive, the preferred base metal 10 of this laminated metal structure is stainless steel, and more preferably 12% Cr stainless steel.
  • The buttering layer 20 in a soft material having a thermal expansion coefficient between that of the base metal and that of the hard-surfacing layer. Preferably, the buttering layer consists essentially of nickel, a nickel-based alloy, or a mixture of these. The buttering layer 20 is bonded, preferably welded, to the base metal 10. The buttering layer 20 also adds to the overall strength of the structure, since the bond between the hard-surfacing layer 30 and the base metal 10 may not be strong enough by itself to keep a multi-layer hard-surfacing deposit from pulling off. See T. B. Jefferson, et al., Metals and How to Weld Them, pp. 297, 298.
  • The buttering layer is selected to be a relatively soft material to withstand the shock of the thermal expansion caused by the heat of the welding procedures. Nickel and its alloys are as the preferred metals for the buttering layer 20 of this invention because the coefficient of thermal expansion of these materials is in-between that of the preferred 12% Cr base metal and the preferred hard-surfacing materials. Nickel and nickel alloys are additionally preferred because of their excellent resistance to corrosion and oxidation even at high temperatures and because they permit an overlay of the preferred hard-surfacing materials without significant cracking. Additionally, the buttering layer 20 should also contain above about 12% chromium by weight. This prevents the diffusion of chromium from the 12% Cr stainless steel into the weld deposit during welding and preserves the corrosion resistance of the base metal 10.
  • One important alloy that can be used for this purpose is MONEL (RTM), which is 67% nickel, 28% copper and 5% manganese and silicon combined. MONEL is especially valuable where the turbine components are subject to wear and corrosion. Also useful are the heat-hardened variations of MONEL such as, K MONEL, H MONEL, S MONEL, R MONEL and N MONEL. The most preferred material for the buttering layer 20 is INCONEL (RTM) which is a nickel-chromium alloy. Of particular interest to the purposes of this invention, is the material INCONEL-82, ASME SF 5.14, class ERNICR-3, which material exhibits the following composition by weight percent: C (0.1); Mn (2.5-3.5); Fe (3.0); P max (0.03); S max (.05); Si (0.5); Cu max (0.5); Ni min (67.0); Co max (0.1); columbium and tantalum (2.0-3.0); Ti max (0.75); tantalum (0.3); and Cr (18.0-22.0). The buttering layer 20 generally has a thickness of about 0.25 mm to 5.0 mm, more preferably about 2 mm. This thickness can be attained by machining the layer after bonding to the base metal.
  • The material selected for the hard-surfacing layer 30 should have a Rockwell hardness reading significantly higher than that for the base metal, preferably in the range of 30-55 HRC. In general, the choice of hard-surfacing materials can be made on the basis of service requirements and the nature of wear and other conditions that are expected. Typical hard-surfacing alloys useful for this invention include chromium carbide, tungsten carbide, high-carbon chromium alloy, austenitic manganese, austenitic stainless steel (chromium-nickel types), high-speed tool steels, air or oil hardening tool steels, medium carbon and alloy steels, cobalt-based hard-surfacing materials and nickel-based hard-surfacing alloys. The hard-surfacing alloys preferably comprise cobalt to impart to the finished turbine component high hardness at elevated temperatures. The most preferred materials are TRIBALOY-400 and STELLITE-6, the former being selected as a preferred material for stationary turbine components and the latter being preferred for moving turbine components. While STELLITE-6 is conventional, TRIBALOY-400 is a relatively new alloy consisting essentially of .02 weight %C; 2.6 weight %Si; 8.5 weight %Cr; 28.5 weight %Mo; 3.0 weight %Ni and Fe; and the balance being Co. These materials have been selected for example only, and those skilled in the art may find various alloy substitutions exhibiting similar properties. The hard-surfacing layer of this invention preferably has a thickness of about 1.27 to 6.35 mm, and more preferably about 4.57 mm.
  • The buttering layer 20 and hard-surfacing layer 30 can be bonded to or disposed on the base metal 10 by any mechanical, metallurgical, or chemical means known to those in the metal-working industry. Preferably, the buttering layer 20 is weld deposited to the base metal layer and the hard-surfacing layer 30, in turn, is weld deposited to the buttering layer. Typical coating processes that can be employed for this purpose include: Thermal Spraying, Plasma Transferred-Arc, Shielded Metal Arc, MIG, or TIG procedures. The most preferred welding process is TIG (Tungsten-Inert-Gas). Below, is a detailed summary of the preferred basic parameters for applying the preferred buttering layer 20, INCONEL-82, and the preferred hard-surfacing layer, TRIBALOY-400, using a TIG welding process:
    Figure imgb0001
  • In a preferred method, INCONEL-82 is welded to the base metal, using the above procedure, to provide a buttering layer thickness of about 2.54 mm. The buttering layer is preferably machined to a thickness of about 2.03 mm. The resultant intermediate composite, which comprises the base metal and buttering layer, is then heated to a temperature of about 232°C to 482°C, preferably about 400°C, prior to and during the welding of the hard-surfacing layer 30 onto buttering layer 20. As used herein, the temperature of the substrate during the welding of the hard-surfacing layer 30 is referred to as the "interpass temperature".
  • Preheating is useful to (1) minimize the possibility of thermal shock damage to the stainless steel as the welding arc is applied; (2) slow the cooling to prevent the formation of excessively large fusion zones; (3) prevent excessive hardness in the weld itself; and (4) equalize the cooling of the weld and the base metal, thereby minimizing the possibility of shrinkage cracks. See T. B. Jefferson, et. al., Metals and How to Weld Them, p. 332.
  • After depositing the hard-surfacing material, the laminated metal structure is preferably tempered with a post-weld heat treatment. When the base metal 10 is the preferred 12% Cr stainless steel, the temperature selected for the post-weld heat treatment should be high enough to temper martensite formations in this base metal. The preferred heat treatment schedule comprises heating the welded structure for a time that is sufficient to relieve at least the maximum stresses caused by the various bonding steps of the method. A preferred heat treatment range is from 593°C to 627°C.
  • The laminated metal structure 100 resulting from the bonding operation, as described, is generally at a temperature of about 232-482°C. The structure can be permitted to cool in an insulating atmosphere, or maintained at about its interpass temperature prior to insertion into a heat-treating oven. The laminated metal structure 100 is then heated at about 30-40°C per hour, preferably about 38° per hour, until is obtains a uniform temperature of about 593°C to 627°C. The structure 100 is then held at that temperature for about 1 to 3 hours. Preferably, the structure is held at the optimum temperature for one hour per inch of thickness of the component, with one hour being the minimum holding time for pieces under one inch in thickness. After heat treatment, the component is preferably allowed to cool at a rate below about 38°C per hour. This can be accomplished by cooling in an insulating environment, i.e., Vermiculite, Kaowool or a slow furnace rate cooling. This cooling step is continued at least until the laminated metal structure 100 obtains a uniform temperature of about 149°C, at which point the cooling rate is less important and the structure can be exposed to ambient temperatures. It must be noted that this heat treatment schedule is for illustrative purposes only, and those skilled in the art may find alternative heat treatment schedules that will provide sufficient tempering for both the weldment and the heat-affected zone of the base metal.
  • In summary, this invention provides a turbine component having a laminated metal structure 100 exhibiting fewer imperfections, while at the same time, maintaining resistance to wear from room temperature to elevated temperatures. The preferred combination of INCONEL 82 and TRIBALOY 400 produces a surface having a Rockwell "C" hardness reading of about 40-50. The INCONEL 82 buttering layer possesses a coefficient of thermal expansion intermediate to that of the base metal and the preferred hard-surfacing material, TRIBALOY-400. INCONEL 82 also consists of 18.0 to 22.0 weight % Cr which permits the deposition of this alloy with minimal dilution of the chromium content of the stainless steel base metal. Finally, the turbine component having a laminated metal structure of this invention is readily fabricated using existing welding procedures and provides for longer lasting turbine components.
  • This structure is particularly useful in minimizing cracking and the service life of stainless steel keys and liners located on the flow guides of steam turbine systems. These components can be coated with a nickel-containing, buttering layer, of the kind described above, then hard-surfaced. Accordingly, the elevated temperature turbine system, thus protected, can be operated with less downtime due to replacement of these critical parts.
  • From the foregoing, it can be realized that this invention provides an improved turbine component having a laminated metal structure and method for resisting wear at elevated temperatures. The turbine component having a laminated metal structure utilizes a novel buttering layer which provides a buffer and limits the thermal shock caused by the welding processes. Accordingly, this invention provides a sounder hard-surfacing weldment and specifically, a more economical TRIBALOY application procedure without a high rejection rate due to cracking of weld deposits.

Claims (5)

  1. A turbine component having a laminated metal structure for resisting wear at elevated temperatures which comprises a base metal comprising stainless steel containing 8 to 16 weight percent chromium, a buttering layer welded to said base metal and containing nickel, a nickel-based alloy or a mixture thereof and welded to said buttering layer a hard-surfacing layer comprising cobalt for protecting said base metal from wear at elevated temperatures, and having a macro-hardness of at least 30 HRC, characterized in that said buttering layer includes chromium in an amount of at least 12 weight % and said hard-surfacing layer combining with said buttering layer to form a coating substantially free of welding-induced cracks.
  2. A turbine component according to claim 1, characterized in that the base metal comprises 12 weight % chromium.
  3. A turbine component according to claim 1 or 2, characterized in that the hard-surfacing layer consists of about 0.02 weight % C, 2.6 weight % Si, 8.5 weight % Cr, 28.5 weight % Mo, 3.0 weight % Ni and Fe, and the balance being Co.
  4. A turbine component according to claim 1, 2 or 3, characterized in that the buttering layer has a thickness of from 0.25 to 5 mm.
  5. A turbine component according to any of claims 1 to 4, characterized in that the hard-surfacing layer has a thickness of from 1.27 to 6.35 mm.
EP88305747A 1987-06-22 1988-06-22 Improvements in or relating to laminated metal structures for resisting wear at elevated temperatures Expired - Lifetime EP0296861B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/064,721 US4814236A (en) 1987-06-22 1987-06-22 Hardsurfaced power-generating turbine components and method of hardsurfacing metal substrates using a buttering layer
US64721 1987-06-22

Publications (2)

Publication Number Publication Date
EP0296861A1 EP0296861A1 (en) 1988-12-28
EP0296861B1 true EP0296861B1 (en) 1993-03-31

Family

ID=22057859

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88305747A Expired - Lifetime EP0296861B1 (en) 1987-06-22 1988-06-22 Improvements in or relating to laminated metal structures for resisting wear at elevated temperatures

Country Status (8)

Country Link
US (1) US4814236A (en)
EP (1) EP0296861B1 (en)
JP (1) JPS6422470A (en)
KR (1) KR890000674A (en)
CN (1) CN1021308C (en)
CA (1) CA1295096C (en)
ES (1) ES2040858T3 (en)
YU (1) YU112888A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3725457B1 (en) * 2019-04-17 2024-07-03 General Electric Technology GmbH Turbine casing component and repair method therefor

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002839A (en) * 1989-10-16 1991-03-26 Westinghouse Electric Corp. Hardfacing processes for valve components
US5024582A (en) * 1990-08-14 1991-06-18 Westinghouse Electric Corp. Steam turbine rotor having graded weldments
FR2675415B1 (en) * 1991-04-22 1995-06-30 Creusot Loire STAINLESS STEEL SHEET AND PROCESS FOR PRODUCING THE SAME.
US5248241A (en) * 1991-10-21 1993-09-28 Southern California Edison Co. Components made of hardenable and non-hardenable materials
US5496046A (en) * 1992-03-22 1996-03-05 Brandon; Ronald E. Turbine seal rub protection means
TW340078B (en) * 1995-07-06 1998-09-11 Showa Sentetsu Kk Process of manufacturing rion-copper substrate coating welding containing metal-mesh intermediate layers
US6164916A (en) * 1998-11-02 2000-12-26 General Electric Company Method of applying wear-resistant materials to turbine blades, and turbine blades having wear-resistant materials
CA2537506C (en) * 2003-09-03 2009-12-15 Fluor Technologies Corporation Post weld heat treatment for chemically stabilized austenitic stainless steel
CN1314534C (en) * 2004-03-12 2007-05-09 应卫忠 Multilayer composite patterned stainless steel and its mfg. method
US7371988B2 (en) * 2004-10-22 2008-05-13 Electric Power Research Institute, Inc. Methods for extending the life of alloy steel welded joints by elimination and reduction of the HAZ
US7687151B2 (en) * 2005-04-12 2010-03-30 General Electric Company Overlay for repairing spline and seal teeth of a mated component
US7591057B2 (en) * 2005-04-12 2009-09-22 General Electric Company Method of repairing spline and seal teeth of a mated component
US20070269676A1 (en) * 2006-05-19 2007-11-22 Singer Kevin M Diffusion barrier layer and method of making the same, and wear resistant article with the diffusion barrier layer and method of making the same
EP1892091A1 (en) * 2006-08-25 2008-02-27 Siemens Aktiengesellschaft Turbine blade with protective coating and buttering layer
DE102007035009A1 (en) 2007-07-26 2009-02-05 Asanov, Ibragim Method for providing a coating
US8708655B2 (en) 2010-09-24 2014-04-29 United Technologies Corporation Blade for a gas turbine engine
JP5785376B2 (en) * 2010-10-19 2015-09-30 株式会社東芝 Overlay welding method
CN102785035A (en) * 2012-07-27 2012-11-21 林淑琴 Repair welding process for camshaft of internal combustion engine
CN102785435A (en) * 2012-08-10 2012-11-21 昆山乔锐金属制品有限公司 Metal-ceramic composite material
KR20160051895A (en) * 2013-09-30 2016-05-11 제이에프이 스틸 가부시키가이샤 Friction stir welding method for steel sheets and method of manufacturing joint
WO2015066418A1 (en) 2013-10-31 2015-05-07 Vermeer Manufacturing Company Hardfacing incorporating carbide particles
WO2016016717A1 (en) * 2014-07-31 2016-02-04 Sabic Global Technologies B.V. Repair of sigmatized stainless steels
JP7225501B2 (en) * 2018-04-14 2023-02-21 エーエムエル3ディー・リミテッド Method and apparatus for manufacturing 3D metal parts
JP7160694B2 (en) * 2019-01-08 2022-10-25 日立Geニュークリア・エナジー株式会社 FLUID CONTACT MEMBER AND METHOD FOR MANUFACTURING FLUID CONTACT MEMBER
US20220331914A1 (en) * 2021-04-15 2022-10-20 General Electric Company Methods of coating components with cold spray and brazing coated components
CN113369639A (en) * 2021-06-30 2021-09-10 江西恒大高新技术股份有限公司 Preparation method of ultrathin ultralow-dilution-rate high-temperature alloy cladding layer for garbage incinerator

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755887A (en) * 1971-11-12 1973-09-04 Continental Can Co Method of making cobalt alloy steel composite article
US3804602A (en) * 1971-11-12 1974-04-16 Continental Can Co Cobalt alloy steel composite article
US4418124A (en) * 1980-10-06 1983-11-29 General Electric Company Plasma spray-cast components
JPS57185990A (en) * 1981-03-17 1982-11-16 Hitachi Metals Ltd Coating method for alloy
JPS58212869A (en) * 1982-06-03 1983-12-10 Ishikawajima Harima Heavy Ind Co Ltd Surface-hardening build-up welding method of stainless steel
US4677034A (en) * 1982-06-11 1987-06-30 General Electric Company Coated superalloy gas turbine components
JPS60206567A (en) * 1984-03-30 1985-10-18 Ebara Corp Formation of corrosion- and wear-resistant build-up layer
US4665996A (en) * 1986-03-31 1987-05-19 Exxon Production Research Company Method for reducing friction in drilling operations

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3725457B1 (en) * 2019-04-17 2024-07-03 General Electric Technology GmbH Turbine casing component and repair method therefor

Also Published As

Publication number Publication date
CA1295096C (en) 1992-02-04
KR890000674A (en) 1989-03-16
EP0296861A1 (en) 1988-12-28
YU112888A (en) 1990-04-30
JPS6422470A (en) 1989-01-25
CN1031201A (en) 1989-02-22
ES2040858T3 (en) 1993-11-01
US4814236A (en) 1989-03-21
CN1021308C (en) 1993-06-23

Similar Documents

Publication Publication Date Title
EP0296861B1 (en) Improvements in or relating to laminated metal structures for resisting wear at elevated temperatures
US4219592A (en) Two-way surfacing process by fusion welding
US6337459B1 (en) Multi-layered anti-coking heat resisting metal tube and the method for manufacturing thereof
US4803045A (en) Cobalt-free, iron-base hardfacing alloys
US4940390A (en) Turbine system having more failure resistant rotors and repair welding of low alloy ferrous turbine components by controlled weld build-up
EP1164180B1 (en) Multi-layered anti-coking heat resistant metal tube and method for manfacturing thereof
US20100101780A1 (en) Process of applying hard-facing alloys having improved crack resistance and tools manufactured therefrom
US20150275341A1 (en) Non-magnetic metal alloy compositions and applications
US4216015A (en) Wear-resistant iron-nickel-cobalt alloys
CA1283056C (en) Hardfacing technique and improved construction for inlet steam sealingsurfaces of steam turbines
US4942059A (en) Method for hardfacing metal articles
JPH04224207A (en) Surface treatment method for steam turbine member
US5704765A (en) High chromium content welding material to improve resistance of corrosion method and device
US4659632A (en) Cobalt alloy for build-up welding having improved resistance to weld crack
EP0634245B1 (en) Wear resistant alloy
JPS6221465A (en) Double layer padding method to aluminum base metal
Smart Selection of surfacing treatments
Sankarapandian et al. Microstructure, Mechanical Properties, and Corrosion Behavior of Co‐Based Stellite 6 Multilayer Overlays Deposited on ASTM A36 Steel by Gas Metal Arc Welding Process
Henderson et al. Alloy classification of hardfacing materials
CN1080769C (en) A cylinder member and nickel-based facing
JPH08215842A (en) High temp. sliding member
Mellor Welding surface treatment methods for protection against wear
Mishler et al. Welding of high-strength steels for aircraft and missile applications
Andrews Building-up and Hard Surfacing by Welding
Bunch et al. Corrosion/Galling Resistant Hardfacing Materials for Offshore Production Valves

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE ES FR IT

17P Request for examination filed

Effective date: 19890627

17Q First examination report despatched

Effective date: 19910730

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE ES FR IT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930415

Year of fee payment: 6

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19930621

Year of fee payment: 6

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2040858

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19940513

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19940630

BERE Be: lapsed

Owner name: WESTINGHOUSE ELECTRIC CORP.

Effective date: 19940630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19950623

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19991007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050622

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19940630